Process for preparing oxyalkylated derivatives with alkylene carbonates



United States Patent PROCESS FOR PREPARING OXYALKYLATED DE- RIVATIVES WITH ALKYLENE CARBONATES Louis T. Monson, Puente, and Woodrow J. Dickson,

vMonterey Park, Califi, assignors to Petrolite Corporation, Los Angeles, Califi, a corporation of Delaware No Drawing. Original application June 4, 1953, Serial No. 359,661, now Patent No. 2,819,261, dated January 7, 1958. Divided and this application July 3, 1957, Serial No. 669,713

4 Claims. (Cl. 260-473) This invention relates to the preparation of substantially anhydrous and substantially undiluted oxyalkylated derivatives of a particular class of oxyalkylation-susceptible organic compounds which, because of certain characteristics they possess, are not otherwise oxyalkylatable to'produce such derivatives.

oxyalkylation-susceptible organic compounds are characterized by their possession of labile hydrogen atoms, i.e., hydrogen atoms attached to oxygen, nitrogen, or sulfur. Their oxyalkylation may proceed with greater or lesser readiness; but oxyalkylated derivatives can be prepared from them.

The oxyalkylating agents conventionally employed to produce oxyalkylated derivatives are the lower alkylene oxides, ethylene oxide, propylene oxide, butylene oxide, glycid, and methylglycid. These may be defined as alphabeta alkylene oxides containing four carbon atoms or less. They may be employed singly, in sequence, or in admixture.

Unfortunately, there are some situations, like those with which this invention is concerned, in which the employment of such conventional oxyalkylating agents is not practicable. Some starting materials, although inherently oxyalkylation-susceptible,' a-re solids which are substantially insoluble in any of the oxyalkylation-resistant solvents available for use in the preparation of oxyalkylated derivatives.

For example, many oxyalkylation-susceptible solids are insoluble in xylene, which is a frequently used solvent in oxyalkylation procedures. Xylene is oxyalkylation-resistant'and is readily separable from the oxyalkylation mass by simple distillation.

' Furthermore, even though such starting materials may be soluble in a few unusual oxyalkylation-resistant solvents, the latter are themselves comparatively non-volat'ile. Various ethers might in some cases be considered suitable solvents for the oxyalkylatiomsusceptible solid starting material. Such ethers, like the diethers of the polyglycols, in addition to being expensive, are not susceptible to easy separation from the oxyalkylation mass by distillation. Hence, they are not readily recoverable from the oxyalkylation mass by distillation, to leave an undiluted oxyalkylated derivative.

Some solids which are oxyalkylatiou-susceptible are in fact most soluble in water; but water is not an acceptable solvent for use in oxyalkylation processes employing the conventionally used alkylene oxides because it reacts with such alkylene oxides to produce polyglycols, during oxyalkylation.

We are aware that it has been proposed in the past to conduct oxyalkylations using the conventional alkylene oxides in aqueous solutions, presumably on the assumption that the oxide did not react with the water. However, it is now established that such reaction with the water occurs to some extent. The oxyalkylated mass produced in such aqueous systems therefore contains varying proportions of alkylene glycols as contaminants or adulterants. Our process avoids this ditficulty because it is conducted under substantially anhydrous conditions in all cases. The starting solid material, the catalyst, and the alkylene carbonates are all employed by us in substantially anhydrous form.

Furthermore, many oxyalkylation-susceptible solids cannot be used in undiluted form in an oxyalkylation process using the alkylene oxides, and simply liquefied by heating prior to introduction of the oxyalkylating agent, because they undergo partial decomposition as they melt. If maintained at the temperature at which fusion just begins to be apparent, for a time such as 15 minutes, they undergo at least partial decomposition. If they exhibit such behavior in the presence of an oxyalkylation catalyst, like the alkali carbonates, they come within our class of suitable starting'materials for use in our present process.

The foregoing statement of difficulties is applicable to greater or lesser extent to a number of oxyalkylation-susceptible compounds, including those recited below. The alkylene oxides are not usable for their oxyalkylation for the above stated reasons.

Our present invention overcomes such difliculties and permits oxyalkylation of such materials to be accomplished by simple and inexpensive means. Thus, we employ as primary oxyalkylating agents the carbonates which are the counterparts of the foregoing alkylene oxides, viz., ethylene carbonate, propylene carbonate, butylene carbonate, hydroxypropylene carbonate, and hydroxybutylene carbonate. Of these, only ethylene carbonate and propylene carbonate are currently in commercial production, although the others will doubtless achieve similar commercial status in time.

More specifically, our invention relates to a two-step process for preparing substantially anhydrous, substantially undiluted oxyalkylated derivatives from a tannin, which process consists in: (A) first reacting said solid with at least one alkylene carbonate selected from the class consisting of ethylene carbonate, propylene carbonate, butylene carbonate, hydroxypropylene carbonate, and hydroxybutylene carbonate, in presence of an oxyalkylation catalyst; the proportion of alkylene carbonate employed being suificient to yield a product which is at least liquefiable at the temperature required to effect its'subsequent oxyalkylation using at least one alkylene oxide selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycid, and methylglycid; and (B) subsequently reacting such partially oxyalkylated derivative with at least one member selected from the aforesaid class of alkylene oxides.

Briefly described, our process is practiced by introducing into a suitable processing vessel the solid, oxyalkylation-susceptible starting material, preferably in finely divided form; the desired or required proportion of alkylene carbonate; and a minor proportion of an alkaline catalyst such as an alkali carbonate. The mixture is warmed, preferably with stirring. As the temperature reaches a certain critical level, usually somewhat above C., there is a vigorous effervescence in which carbon dioxide is liberated, and the oxyalkylated derivative is formed.

In such instances where the starting material is acidic, it is used at least partially in the form of a salt, e.g., an alkalisalt such as may be produced in situ by adding enough alkaline catalyst to leave a slight excess over what is required to leave the mixture slightl alkaline.

It is sometimes desirable to modify this general procedure in various minor ways. For example, the alkylene carbonate is introduced into a vessel and warmed until liquid. The catalyst is added. The solid, oxyalkylation-susceptible material is then slowly introduced in finely divided form, with stirring, and the temperature I using the ides. Y

' properties; I I Y Y Y i As is true of all generally applicable processes, We.

have found that all oxyalkylationrsusceptibleistarting ma- I I terials of the defined class do not react with equal- =readiness with I the alkylene carbonates in our process. Where the starting material, although presumably oxy 'alkylation-susceptible as judged by its structure, is of In our process, we usually employ onlygenou'gh alkyle 'ene carbonate in the first step :to; produce a liquid or readily liiquefiahle derivativewhich contains, a, relatively I small proportion of oxyalkylene radicals. We then con- ,tinue oxyalkylation using the conventional alkylene ox-v ides. I Stated another way, this two-step process is ern- Y ployed to produce,first, intermediates; then more highly :oxya'lkylated products are prepared in: the second stepi i more economical; conventional alkylene ox-r vintheappended claims,- we have specified that: the

I 2 intermediate product prepared in I the first step of the I Y two-step process shall be a liquidior atleast liquefiable atthe temperature required to effect the oxyalkylation by i use of the alkylene I oxides: more second: step .ofour process; Said second; step is conducted at conventional I oxyalkl-ation temperatures, usually between about 100 "(Land 200C. I Y i. Y' One incidental advantage of using the alkylene ;car-; 7 bonates foroxyalkylation is that they. are relatively inert Y 3 materials as compared with the alkyleneoxides. Their use] therefore entails, smaller, hazards. Oxyalkylations' i usingthem are conducted with greater safety thanv if the I I alkylene oxides were employed. Processing vessels are usually- 'not requircd to be :pressure resistant when the; I, alkylene carbonates-are employed, whereas ethylene o'xi ide and propylene Y oxide, for example, are rtsquirccl to pressure vessels "because of their physical be employed in very high molecular weight, or where steric or other obscure influences are adverse, oxyalkylation may proceed at extremely slow rates. However, if the starting material is oxyalkylation-susceptible, its oxyalkylation maybeaccomplished in due time by means of the alkylene carbonates mentioned above.

The temperature at whichthe oxyalkylation reaction will occur, using the alkylene carbonates, must be ex pected to vary somewhat with the choice of starting material. In all cases, the proper technique to be initially employedistoadvance the temperature cautiously and so to determine the minimum temperature required to effect reaction. This procedure requires no especial skill and no experimentation, in that the vigorous effervescence resulting from the liberation of carbon dioxide in the reaction is ready evidence of such reaction. As stated above, the reaction usually requires a temperature somewhat above 100 C. The maximum feasible oxyalkylation temperature is of course the decomposition temperature for the mixture of solid starting material, catalyst, and alkylene carbonate, and above which temperature pyrolysis of the starting material, polymerization of the alkylene carbonate, or other undesired reaction begins to occur.

The oxyalkylation catalysts employed by us are usually the alkali carbonates such as sodium or potassium carbonate, in substantially anhydrous form. Where the starting material is acidic, at least sufiicient alkali carbonate should be added to neutralize such acidity. Thereafter an additional amount of alkali carbonate is usually desirably included to accelerate the oxyalkylation process. However, in some instances the alkali-neutralizcd starting material is sufiiciently alkaline to supply the I desired I catalytic. influence,

amountsof'alkali carbonate. I I tThefinished oxyalkylated-product .will of coursc'con- I .tain :such: inorganic catalysts separate readily from the oxyalkylated; mass on stand- I any period of time;

The catalyst will usually ing, especiallyifi slightly warm. Since the residual. pro-.

-portionszof catalyst'in the supernatantproduct: are usually: of, verysmall migitude after: such. setttling,; we.

consider they do, notmaterially dilute or contaminateour finished products. Y

' In' some-instances; solid, oxyalkylation-susceptible; sub;- 1 stances, which; may have-been stated. in the literature to I have definite melting points, I are nevertheless ,susceptia ble' to progressive decomposition if maintained at; or about the temperature at which .theybegin to fuse, for- Sorne such substances similarly undergo progressive deterioration: if subjected to sucl 1 temperatures in. the presence: of an alkaline material, I

like an oxyalkylation catalyst, for periodni time =Snch substances which, although atheyimay have recorded definite melting points, are; unstablev under oxyalkylating conditions as described; are, includedamong our usable I startingmaterials' ;We have therefore limited our iusablestarting .mate- I rialsto those 'which are either (1 infusibleor. which; -(2)- isu'fl'er at least; partial decomposition if maintained:

at their beginningwf-fusion temperature for a'period of I I at least :15. 'minutes in the presence of an oxyalkyl-ation, catalyst. 1 Additionally, such solid starting material must ;be insoluble in oxyalkylation-resistanndistillation-sepa- I I i rable solvents, as alreadystated. I I i 5 I Y As I the molecular weight of; the oxyalkylatiomsuscew tible starting material rises, itsv reactivity with alkylene I carbonates is generally, reduced; Since, for. example, I ethylene. carbonate :is more reactive than propylene care ibonatcand propylene carbonateis morereactiveithan; butylene carbonate, there maybe marked diiferences in the speed of oxylation of such: high-molecular-weight starting materials when; difierent alkylenecarbonates. are: used. ,In marginal cases, it willbe understood, a mate: rial may be oxyalkylation-susceptible in the sense that it is reactive toward ethylene carbonate, but oxyalkylation-inert, in that it is insensitive toward, for example, propylene carbonate or butylene carbonate.

Our process may be practiced using more. than one alkylene carbonate, and in addition, more than one alkylene oxide, to produce mixed oxyalkylated derivatives. In such cases, the alkylene carbonates may be employed in sequence or they may be employed as a mixture, .as desired. The same is true of the alkylene oxides employed in our two-step process, which may housed in sequence or as a mixture.

Asexamples of our process, in which the foregoing starting materials are usable, the following are typical but not exclusive.

In all cases, the apparatus employed to produce the products in the laboratory was a conventional resin pot assembly, fitted with a stirrer. This is a glass apparatus comprising a lower bowl or vessel, and an upper cap section containing several outlets, for the stirrer shaft, a thermometer, and a reflux condenser, and a charge hole fitted with a stopper. The design is conventional and need not be described further. Heat is supplied by a glass-textile heating mantle which fits the lower. portion of the assembly, and which is regulated by inclusion of a rheostat in the electrical circuit. Such devices are likewise wholly conventional, and require no description here. Motor-driven stirrers, of the kind here used, and having stainless-steel or glass shafts and paddles, are likewise conventional laboratory equipment.

Example 1 Heat 40 grams of m-digallic acid (tannic acid) with 264 grams of ethylene carbonate and 5 grams of powwithout addition of further dered sodium carbonate, in a conventional laboratory resin pot assembly, stirring the mixture, and increasing the temperature slowly over a period of about 2 hours, until a vigorous etfervescence occurs, at about 165 C. The catalyst settles to bottom, on standing. The supernatant product is a viscous, dark liquid.

Example 2 Heat 40 grams of commercial quebracho extract with 264 grams of ethylene carbonate and 5 grams of powdered sodium carbonate, in a conventional laboratory resin pot assembly, stirring the mixture, and increasing the temperature slowly over a period of about 1.3 hours, to about 185 C., where efiervescence occurs. After the catalyst settles from the mass, on standing, the supernatant material is a viscous, dark liquid.

Example 3 We have repeated Examples 1 and 2, but substituting 306 grams of propylene carbonate for the 264 grams of ethylene carbonate previously used. Eltervescence occurs as before, as the temperature is increased slowly to about.175-195 C. The products are dark, viscous liquids.

Example 4 Repeat Examples 1 and 2 but substitute 348 grams of butylene carbonate for the 264 grams of ethylene carbonate used in those examples. The products are viscous, dark-colored liquids.

Example 5 Repeat Examples 1 and 2 but substitute 354 grams of hydroxypropylene carbonate for the 264 grams of ethylene carbonate used previously. The products are dark, viscous liquids.

Example 6 Repeat Examples 1 and 2 but substitute 396 grams of hydroxybutylene carbonate for the 264 grams of ethylene carbonate used previously. The products are dark, viscous liquids.

Example 7 Example 9 Heat 40 grams of commercial quebracho extract with a mixture of 132 grams of ethylene carbonate and 153 grams of propylene carbonate and 10 grams of powdered sodium carbonate, in a conventional laboratory resin pot assembly, stirring the mixture, and increasing the temperature slowly over a period of about 2 hours, until H "Ill Ill etfervescence occurs, at about 185 C. The product is a dark, viscous liquid.

Example 10 Transfer the whole reaction mass of Example 9 to a conventional oxyalkylating autoclave. Raise the temperature to between and C. and slowly introduce, with stirring, a mixture of 66 grams of ethylene oxide and 87 grams of propylene oxide, keeping the pressure below about 50 p.s.i. The product is a dark, viscous liquid.

The products of our processes find a number of varied uses, as would be surmised from the variety of compounds embraced within our class of starting materials. They are generally surface-active, and hence are usable where low-surface-tension solutions are useful, as in wetting, dispersing, and emulsifying operations. They are sometimes useful in demulsifying processes, in which oil and water are separated from their emulsions, and particularly crude oil and oil-field waters. They are useful in biochemical and biological work in some cases.

In all cases the practice with respect to the aboverecited examples was to advance the temperature cautiously until etfervescence and evolution of carbon dioxide become apparent. It should be noted that in all cases the reactions of the examples were thereafter continued until the foam produced had substantially subsided. No single time of reaction can be employed, in view of the diversity of the starting materials and the variability in their reactivity.

This is a division of our co-pending application, Serial No. 359,661, filed June 4, 1953, now US. Patent 2,819,261.

We claim:

1. A two-step process for preparing substantially anhydrous, substantially undiluted oxyalkylated derivatives of a tannin, which process consists in: (A) first reacting said tannin with at least one member selected from the class consisting of ethylene carbonate, propylene carbonate, butylene carbonate, hydroxypropylene carbonate, and hydroxybutylene carbonate, in presence of an alkaline oxyalkylation catalyst; the proportion of alkylene carbonate employed being suflicient to yield a product which is at least liquefiable at the temperature required to effect its subsequent oxyalkylation using at least one alkylene oxide selected from the class consisting of ethylene oxide, propylene oxide, butylene oxide, glycide, and methylgylcide; and (B) subsequently reacting such partially oxy alkylated derivative with at least one member selected from the aforesaid class of alkylene oxides.

2. The process of claim 1, wherein the tannin used is tannic acid.

3. The process of claim 1, wherein the tannin used is quebracho extract.

4. The process of claim 1, wherein the tannin used is m-digallic acid.

Carlson Sept-7, 1948 De Groote Jan. 27, 1953 

